CN101855069A - The breathable waterproof garment - Google Patents

The breathable waterproof garment Download PDF

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Publication number
CN101855069A
CN101855069A CN200880116003A CN200880116003A CN101855069A CN 101855069 A CN101855069 A CN 101855069A CN 200880116003 A CN200880116003 A CN 200880116003A CN 200880116003 A CN200880116003 A CN 200880116003A CN 101855069 A CN101855069 A CN 101855069A
Authority
CN
China
Prior art keywords
clothes
fiber net
combination
nanometer fiber
fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200880116003A
Other languages
Chinese (zh)
Other versions
CN101855069B (en
Inventor
J·A·康利
R·A·马林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Safety and Construction Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of CN101855069A publication Critical patent/CN101855069A/en
Application granted granted Critical
Publication of CN101855069B publication Critical patent/CN101855069B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/02—Layered materials
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/10—Impermeable to liquids, e.g. waterproof; Liquid-repellent
    • A41D31/102—Waterproof and breathable
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0205—Uppers; Boot legs characterised by the material
    • A43B23/0235—Different layers of different material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/12—Special watertight footwear
    • A43B7/125—Special watertight footwear provided with a vapour permeable member, e.g. a membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
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    • B32B5/024—Woven fabric
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    • B32B5/028—Net structure, e.g. spaced apart filaments bonded at the crossing points
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    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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    • B32B7/04—Interconnection of layers
    • B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
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    • B32B2437/00—Clothing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/24998—Composite has more than two layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Multi-Layer Textile Fabrics (AREA)

Abstract

The present invention relates to comprise the clothes of breathable layered product, described layered product randomly is attached to outer fabric and optional internal layer fabric.Described breathable layered product is formed by the microporous barrier structure, and described microporous barrier is in face-to-face relation with nanometer fiber net and randomly combines with nanometer fiber net.

Description

The breathable waterproof garment
The cross reference of related application
Present patent application is compiled the 119th according to United States code the 35th, requires the priority of U.S. Provisional Application 61/002,796 (being filed on November 13rd, 2007), and its disclosure is incorporated this paper into all purposes shown in being used for way of reference.
Invention field
The present invention relates to comprise ventilative and clothes watertight composition, and relate to the structure of described layer.
Background of invention
As everyone knows, the film that mixes ventilative and waterproof in clothes can make the clothes waterproof when giving the clothes gas permeability, thereby allows the user feel more comfortable.For example expanded polytetrafluoroethyl, ne (ePTFE) film has been used in this application.
As time goes on, the dirt of health grease and effluent form can stop up the hole in the film, thereby has a strong impact on the performance of film.People once attempted allowing polymer that water vapour passes through so that this film is protected by applying to described film, but this can cause the gas permeability of clothes to descend.Therefore, need between life-span and comfortableness, weigh.
The structure that material of the present invention is intended to solve this type of problem and resistant dirt, highly breathable are provided.
Summary of the invention
In one embodiment, the present invention relates to have the outside and the clothes that comprises the inboard of breathable layered product and outer fabric, described breathable layered product comprises the microporous barrier that is in face-to-face relation with nanometer fiber net.
Detailed Description Of The Invention
When term " outside " when being used to describe the position of layer, it is meant towards the garment surface away from wearer's direction.Term " interior " is meant the side towards the user.
Term " layers of nanofibers " and " nanometer fiber net " are used interchangeably in this article.Nanometer fiber net is the non-woven material that comprises nanofiber.
As used herein, " nanofiber " is meant to have less than about 1000nm even less than about 800nm even between between about 50nm and the 500nm and even the number average diameter between about 100nm and 400nm or the fiber of cross section.As used herein, term " diameter " comprises the maximum cross section of non-circular shape.
So-called " clothes " is meant any object of being avoided other factor affecting in weather or the external environment by user's dress with some position of protection user health.For example overcoat, jacket, trousers, cap, gloves, shoes, socks and shirt all are considered to meet the clothes of this definition.
Term " non-woven material " is meant the fleece of the fiber that comprises many random distribution.Fiber can be bonded to each other usually, perhaps can not combination.Fiber can be short fiber or continuous fiber.Fiber can comprise a kind of material or multiple material, also can be the combination of different fibers or the combination that comprises the like fibrous of different materials respectively.
" calendering " is to make fleece pass the process of two roll gaps between the roller.Roller can contact with each other, and perhaps fixing or variable gap can be arranged between the roller surface." patternless " roller is meant the roller that has smooth surface in the process of making them.When fleece passed roll gap, point or pattern did not make and can specially generate pattern on fleeces, and this is different from a little in conjunction with roller.
Clothes of the present invention comprises composite fiber web, and this composite fiber web is made by the nanometer fiber net that one or more layers of nanofibers combine with microporous barrier.Can be by nanometer fiber net being laminated on the film with adhesive, or prepare this combination in the mode that forms film/layers of nanofibers structure by in the nanometer fiber net spinning technique, directly on film, forming layers of nanofibers.Mode that can also mechanical interlocking adheres to layers of nanofibers on the film.The example of film can comprise multiple microporous barrier, for example polymer of the filling of La Shening and expanded polytetrafluoroethyl, ne (ePTFE), to the use of film without limits, as long as layers of nanofibers is added in the substrate.
As-spun nanoweb mainly comprises or only comprises nanofiber, nanofiber can be easily by for example traditional electrostatic spinning of electrostatic spinning or electricity blows and be prepared by meltblown or other this type of method that is suitable in some cases.Traditional electrostatic spinning is the United States Patent (USP) 4,127 that is incorporated herein in full, and the technology described in 706 wherein applies high voltage to generate nanofiber and non-woven mat to polymer solution.Yet the total productive capacity in the electrostatic spinning method is too low, so that can't commercially produce the fleece of heavier basic weight.
" electricity blows " method has disclosed in world patent announcement WO 03/080905, and it incorporates this paper into way of reference in full.The polymer solution flow that comprises polymer and solvent is sent to a series of spinning-nozzles of spinning head from storage tank, be applied with high voltage to nozzle, and polymer solution is therefrom by discharging.Simultaneously, the compressed air of optional heat is discharged by air nozzle, and this air nozzle is arranged in the side of spinning-nozzle or on the periphery.Usually the guiding air is to form blowing gas stream downwards, and blowing gas stream wraps the polymer solution of new discharge and makes it forward, and helps to form fleece, and fleece is collected on the ground connection porous collecting belt of vacuum chamber top.Electricity blows the feasible nanometer fiber net that can form commercial-sized and quantity in the short relatively time cycle of method, and its basic weight surpasses about 1gsm, even up to about 40gsm or bigger.
Can on gatherer, arrange substrate or scrim, to collect and to be combined in spun nanometer fiber net in the substrate.The example of substrate can comprise multiple non-weaving cloth, and for example melt-blowing nonwoven, acupuncture or hydro-entangled non-woven fabric, woven cloths, looped fabric, paper wood etc. use without limits it, as long as layers of nanofibers can be added in the substrate.Non-weaving cloth can comprise spun-bonded fibre, dry-laying or wet-laying fiber, cellulose fibre, meltblown fibers, glass fibre or their blend.
The polymeric material that can be used for forming nanometer fiber net of the present invention is not specifically limited, it comprises addition polymers and condensation polymer material, the for example polysulfone polymer of polyacetals, polyamide, polyester, polyolefin, cellulose ether and ester, polyalkylene sulphur, poly (arylene ether) oxygen, polysulfones, modification, and their mixture.Preferable material comprises poly-(vinyl chloride), polymethyl methacrylate (with other acrylic resins), polystyrene and their copolymer (comprising ABA block polymer) of crosslinked and the non-crosslinked form, different hydrolysis degree (87% to 99.5%), poly-(vinylidene fluoride), poly-(vinylidene chloride), polyvinyl alcohol in these kinds.Preferred addition polymers tends to glassware (Tg is greater than room temperature).The Kynoar of the composition of polyvinyl chloride and polymethyl methacrylate, poly styrene polymer or alloy or low-crystallinity and polyvinyl alcohol material are like this.The preferred polyamide polycondensate of one class is a nylon material, for example nylon-6, nylon-6,6, nylon 6,6-6,10 etc.When forming polymeric nanofiber web of the present invention by meltblown, can use to melt and spray any thermoplastic polymer that forms nanofiber, comprise polyolefin, for example polyethylene, polypropylene and polybutene; Polyester, for example poly-(PETP); And polyamide, for example top listed nylon polymer.
Adding plasticizer known in the art in above-mentioned multiple polymers is favourable so that reduce the Tg of fibre-forming polymer.The plasticizer that is fit to depends on the polymer that blows by electrostatic spinning or electricity, and depends on the final application that nanometer fiber net is concrete.For example, nylon polymer available water or even come plasticising with the residual solvent in electrostatic spinning or the electroblowing process.Other plasticizer known in the art that can be used for reducing polymer Tg include but not limited to aliphatic glycols, aromatics sulfamido, phthalate, wherein phthalate includes but not limited to that those are selected from following compound: dibutyl phthalate, DHP, dicyclohexyl phthalate, dioctyl phthalate, diisooctyl phthalate, two 11 esters of phthalic acid, didodecyl phthalate, and diphenyl phthalate etc.Edited by George Wypych, " the TheHandbook of Plasticizers " of Chemtec publication in 2004 incorporates this paper into way of reference, and it discloses and can be used for other polymer/plasticizer combinations of the present invention.
As-spun nanoweb of the present invention can stand to roll so that give required physical characteristic for fabric of the present invention, as be filed in the common unsettled U.S. Patent application 11/523 on September 20th, 2006, disclosed in 827, this patent application is incorporated this paper into way of reference in full.As-spun nanoweb can be fed in the roll gap between two pattern-free rollers, one of them roller is patternless soft roller, another roller is patternless hard roller, the temperature of hard roller remains the temperature between Tg and Tom, wherein this paper is defined as the temperature that polymer is stood when rubbery state changes by vitreousness with Tg, temperature when Tom is defined as polymer and begins fusion makes the nanofiber of nanometer fiber net be in mecystasis when passing rolling nip.The composition of roller and hardness can change to generate the final serviceability of required fabric.A roller can be hard metal, for example stainless steel; Another roller is the roller of soft metal or polymer-coated or the hardness composite roll less than Rockwell B 70.The time of staying in the roll gap of fleece between two rollers is controlled by fibroreticulate linear velocity, and described linear velocity is preferably between about 1m/min and about 50m/min, and the occupied area between two rollers is the fore-and-aft distance of fleece when contacting simultaneously with two rollers.This occupied area is applied to the pressure at the roll gap place between two rollers and is controlled, and weighs with the power on every linear transverse size of roller usually, preferably between about 1mm and about 30mm.
Non-woven webs can also be stretched, and randomly is heated to simultaneously between the Tg of nanofibre polymer and the temperature between the minimum Tom.Stretching can be before feeding fleece in the stack and/or carries out afterwards, can carry out on vertical or horizontal, or carry out simultaneously on this both direction.
Nanometer fiber net also can comprise antistatic additive.For example, known can by will gather (alkylene ether) glycol add in the condensation mixture as reagent or the polyamide of fusion in obtain antistatic polyamide-based moulded products, for example fiber or long filament are (referring to for example United States Patent (USP) 3,329,557,3,374,288 and 3,966,835; Be filed in Deutsche Bundespatent 1,286,683, belgian patent 631,199, the Swiss Patent 456,029 on January 9th, 1969, their full text is incorporated this paper into way of reference).Make conventional anti-static product by adding for example carbon black, conductive metal fiber, metal dust or ceramic powders as the electrical filler of antistatic conductive, to strengthen their effective antistatic property.The said goods has the high advantage of with low cost and electric conductivity and also is applicable among the present invention.
United States Patent (USP) 5,364, the antistatic high molecular weight fibers of modification and the another kind of method of weaving material made disclosed in 582, wherein added low molecular weight amino-alkene of 0.8 to about 2.5 weight % as antistatic additive, to strengthen the picked-up characteristic of antistatic characteristic, uvioresistant photosensitiveness, colouring power and dyestuff.One of ordinary skill in the art appreciates that other antistatic additive also can be used for the present invention.
Can use compound to come nanometer fiber net is further processed, so that its surface has oleophobic property or hydrophobicity.Those skilled in the art should understand compounds suitable for use.The example of this type of processing is for example common U.S. Patent Application Serial Number of transferring the possession of 11/592, Zonyl fluorinated surfactant (DuPont described in 644 (being filed on November 3rd, 2006), Wilmington, DE), the full text of this patent is incorporated this paper into way of reference.
Nanometer fiber net is adjacent with microporous barrier and randomly combine with it.Film can be the PTFE (ePTFE) that expands, or the microporous barrier of any other type known to those skilled in the art.In film used in the present invention, ePTFE can be sintering or unsintered.
Can prepare the ePTFE film by multiple different known method, but preferably prepare ePTFE by expanded ptfe, as United States Patent (USP) 4,187,390,4,110,239 and 3,953, described in 566, above patent is all incorporated this paper into way of reference.So-called " porous " is meant that film has the air penetrability of at least 0.05 cubic meters per minute/square metre (m/min) when the 20mm water gauge.Can use the film that has the 200m/min air penetrability in the 20mm water gauge or when higher.The hole is the micropore that forms between the node of ePTFE and the fibril.
Equally, can use any one described film in the following patent: United States Patent (USP) 5,234,751,5,217,666,5,098,625,5,225,131,5,167,890,4,104,394,5,234,739,4,596,837, and JPA 1078823 and JPA 3-221541, wherein not expansion PTFE that extrude or moulding is heated goods are carried out sintering or half sintering.Then sintering or semi-sintering goods are stretched to form required porosity and required characteristic.
With regard to concrete application, can provide filler material so that at the concrete characteristic that should be used for revising PTFE to PTFE.For example, from United States Patent (USP) 4,949, as can be known, ceramic packing (SiO2) and little glass fibre of limiting the quantity of can be incorporated in the PTFE material in 284; And mentioned that in EP-B-0-463106 titanium dioxide, glass fibre, carbon black, active carbon etc. are as filler.
By highly-filled polymer normally the polyolefin technology for preparing microporous barrier be known.This type of fleece also is suitable as film of the present invention.Usually polyolefinic composition and filler are carried out compounding, and it is pushed and be drawn into film to form microporous barrier, wherein polyolefin is generally polyethylene, and filler is generally CaCO3.
The example that is suitable as the microporous barrier of filter membrane of the present invention comprises United States Patent (USP) 4,472, those that describe in 328,4,350,655 and 4,777,073, and these patents are all incorporated this paper into way of reference.
Microporous barrier and nanometer fiber net can randomly be bonded to each other, and for example by solvent combination, adhesive combination, thermal and ultrasonic wave combination, but also can adopt any method known to those skilled in the art to carry out combination.In a preferred embodiment, it is online to use the lamination that for example is suitable for that film is attached to nanofiber, for example makes material pass through hot roller nip under the temperature that is enough to make the adhesive fusion that is coated on film or the fleece.The surface of one of them roller can have embossing pattern so that form in conjunction with pattern in layered product.
Before carrying out lamination, can use diverse ways adhesive coated with nano fleece or film.For example, at first can use needs regions coated in the adhesive coated with nano fleece, then the ePTFE film is placed on the binder side of institute's coated fabric.Apply conduction heat and enough pressure to the film side, adhesive is flowed in the fenestra.If adhesive is crosslinkable, then adhesive can be crosslinked because be heated, thereby cause the film mechanical attachment in substrate.
Another example of the goods that form as layered product and a kind of laminating method by fluoropolymer and nonfluorinated polymers, United States Patent (USP) 5,855,977 disclose a kind of multi-layer product, and these goods comprise the layer and the fluorinated layer that comprises the fluoropolymer of handing over poly-monomeric unit of nonfluorinated basically.This multi-layer product also comprises aliphatic diamine or polyamines.Compare with the multi-layer product that does not comprise aliphatic diamine or polyamines, aliphatic diamine or polyamines make the adhesiveness between each layer increase.
Can use multiple additive method to improve adhesiveness between fluorinated polymer layer and the polyamide.For example, can between two polymeric layers, add adhesive phase.United States Patent (USP) 5,047,287 disclose a kind of barrier film that is applicable to road vehicle application, this barrier film comprises substrate fabric, this substrate fabric has by adhesive and is attached at least one lip-deep fluororubber layer, and this adhesive comprises and has amino acrylonitrile-butadiene or acrylonitrile-isoprene rubber.
Sometimes also adopt one or two layer is carried out surface treatment and comes secondary combined.For example, some document proposes to handle fluoropolymer layer (for example sided corona treatment) with charged gas atmosphere, and with after-applied one deck second kind of material, for example polyamide thermoplastic.For example, european patent application 0185590 (people such as Ueno) and 0551094 (people such as Krause) and United States Patent (USP) 4,933,060 (people such as Prohaska) and 5,170,011 (Martucci).
In some cases, the blend of fluoropolymer and dissimilar layer self as the intermediate layer, is combined these two layers helping.European patent application 0523644 (people such as Kawashima) discloses a kind of plasticity layered product, and this layered product has polyamide superficial layer and fluororesin surface layer.
In another embodiment of the method that non-fluoropolymer layer is attached to fluoropolymer layer, United States Patent (USP) 6,869,682 have described a kind of goods, these goods comprise the ground floor that combines with the second layer, ground floor is made up of fluoropolymer, and the second layer is made up of the mixture of nonfluorinated polymers, base-material and the crown ether of melt-processable basically.
In another embodiment of the method that non-fluoropolymer layer is attached to fluoropolymer layer, United States Patent (USP) 6,962,754 have described a kind of structure, this structure comprises fluoropolymer layer and is directly connected to the articulamentum of a certain side of fluoropolymer layer, this articulamentum comprises the polyamide binding resin, and this binding resin comes from the condensation of monomer, and described monomer mainly comprises at least a binary acid and at least a diamines of specific composition.
The temperature and pressure that is adopted in the method (for example co-extrusion or lamination) that each layer combined can be enough to the adhesion that provides enough between layer.Yet, may expect the multi-layer product of gained is further processed, for example use additional heat, pressure or both to use simultaneously, so that bigger binder bond strength to be provided between each layer.When by extruding preparation during multi-layer product, a kind of method that additional heat is provided is the cooling that delays layered product after the co-extrusion.Alternatively, can be by each layer being carried out lamination or co-extrusion pressure being higher than only to process under the required temperature of these several assemblies, thus additional heat energy is joined in the multi-layer product.Select as another kind, the finished product layered product at high temperature can be kept the long period.For example, for example baking box or heated liquid are bathed to improve temperature of articles the finished product multi-layer product can be placed independent device.Also can use the combination of these class methods.
The layered product of nanometer fiber net and film is arranged in clothes, and is adjacent with optionally interior tissue layer with outer tissue layer.Multiple natural and synthetic textiles is known and can be used as one or more tissue layer of the present invention, for example is used to make gym suit, durable coat and outdoor goods, protective garment etc. (for example gloves, apron, leather chaps, trousers, boots, moistureproof spat (gators), shirt, jacket, overcoat, socks, footwear, underwear, vest, waders or trousers, cap, rubber gauntlet, sleeping bag, tent etc.).Usually, design is made of loose relatively woven fabric as the clothes of durable coat, this fabric is made by the natural and/or synthetic fibers with relative low-intensity or toughness (for example nylon, cotton, polyester, polyacrylic, polypropylene etc.), every kind of fiber can have less than about 8 gram/daniers (gpd), more typically less than about 5gpd, and in some cases less than hot strength or the toughness of about 3gpd.This type of material can have the multiple beneficial characteristic, for example stainability, gas permeability, brightness, comfort level, and wearability in some cases.
Can use different braiding structures and different counts to form several alternative compound fabrics of weaving, with as composition of the present invention.Braiding structure for example plain weave structure, enhancing plain weave structure (having two or many warps and/or weft yarn), twill structure, enhancing twill structure (having two or many warps and/or weft yarn), satin face structure, the satin face structure that strengthens (having two or many warps and/or weft yarn) all can use.Stretch woven fabrics, checked fabric, dobby fabric and jacquard fabric also are applicable to the present invention.
Alternatively, supatex fabric can be used as outer tissue layer and optionally interior tissue layer.The example of supatex fabric comprises spun-bonded fibre net, meltblown fiber web, multi-direction multilayer carded web, air-flow method fleece, wet method fibre web, the spunlaced and composite fiber web that comprises more than one nonwoven sheet.Suitable spun-bonded fibre net comprises polyolefine fiber, especially polyethylene or polypropylene.This type of polyolefine fiber can comprise other comonomer units of trace.As used herein, term " spun-bonded fibre net " is meant the non-woven webs that is formed by long filament, and these long filaments are extruded, stretch and are deposited on the continuous collection surface.Can carry out combination by any some kinds of methods, method comprises a combination or combination of patterns, under high pressure rolls supatex fabric or make supatex fabric pass saturated chamber.The example of suitable spunbond polyolefine sheet material is for dodging spun polyethylene, and this material can trade name
Figure GPA00001137490100081
Derive from E.I.du Pont de Nemours and Company.
Nanometer fiber net/film layered product can be attached on the part on surface of tissue layer, and can be attached to tissue layer by any way known to those skilled in the art, for example by bonding, heating, use ultrasonic field, loop bonding (stitching) or by the solvent combination.
Can randomly use one or more adhesives nanometer fiber net and microporous barrier or layered product are attached on fabric or the outer fabric.A kind of suitable adhesive is thermoplastic adhesives, and in several times heating and cooling circulation, this adhesive can soften when being heated, then sclerosis when cooling.An example of these type of thermoplastic adhesives is " heat is melted " adhesives.In one embodiment, nanometer fiber net uses for example polyurethane associativity ground combination of solution of polymer adhesive, makes the solvent evaporation then.In another embodiment, when the direct electrostatic spinning of nanometer fiber net was to fabric, the solvent that is spun into nanometer fiber net was used to realize the solvent combination.
Be used for ePTFE rete with porous be pressed onto in adhesive on fabric or the outer fabric can be a kind of of multiple fluorochemical dispersion or synthetic latex also, comprise the moisture anionic dispersions of the terpolymer of butadiene acrylonitrile copolymer, the vinyl chloride for preparing based on the copolymer of acrylate with by the emulsion polymerisation effect and vinylidene chloride polymer copolymer, SB and butadiene, styrene and vinylpyridine.
In one embodiment of the invention, the pad scrim can be inserted between film and the outer tissue layer, and randomly be attached in film and the outer tissue layer one or both." scrim " is supporting layer, and can be can combine, adhere to nanometer fiber net or laminated any plane structure.Advantageously, can be used for scrim layer of the present invention is spunbond nonwoven layers, but can be made by carding fiber net of non woven fibre etc.
Embodiment
For described embodiment herein, use Fu Leize mensuration (ASTM D737) to measure the air penetrability of fabric.In this measuring method, apply the pressure reduction of 124.5N/m2 (0.5 inches of water(in H) to the fabric sample of suitable clamping, the airflow rate that records thus is called the Fu Leize air penetrability, or abbreviates " Fu Leize " as, with m 3/ m 2-min is that unit carries out record.
Fibre diameter is measured in the following manner.5,000 * multiplication factor under, each layers of nanofibers sample is taken ten ESEMs (SEM) image.Can in photo, measure the diameter of ten one (11) individual clear and legible nanofibers, the line item of going forward side by side.Do not comprise defective (that is the portion that joins of lumps of nanofibers, polymer drop, nanofiber).Fiber diameter to each sample is calculated.
For these embodiment, press described in the WO 03/080905,24% polyamide-6,6 formic acid solution is spun into thread by the electricity method of blowing to form nanometer fiber net.The number average fibre diameter is about 400nm.Between nylon and steel rider, nanometer fiber net is rolled.
Table 1 shows four kinds of layered products with nanometer fiber net of 25 micron thickness ePTFE films.Before lamination, randomly nanometer fiber net is rolled.
Table 1
Nanometer fiber net basic weight (gsm) Whether nanometer fiber net through calendering? Fu Leize (m 3/m 2-min)
??9.4 Not ??11.0
??16.4 Be ??4.5
??16.4 Not ??23.0
??16.4 Be ??7.8
With regard to combination, by the intaglio plate applicator roll with solvent-based adhesive (Brookwood CompaniesIncorporated, Wauregan, CT) be coated on the ePTFE, nanometer fiber net is applied on the ePTFE/ binder combination, make then composite with the linear velocity of 21 inch per minute clocks by roll gap and dryer.

Claims (21)

1. have the outside and the clothes that comprises the inboard of breathable layered product and outer fabric, described breathable layered product comprises the microporous barrier that is in face-to-face relation with nanometer fiber net.
2. the clothes of claim 1, wherein said face is to described outer fabric.
3. the clothes of claim 1, wherein said face is to the inboard of described clothes.
4. the clothes of claim 1, described clothes also comprises internal layer fabric.
5. the clothes of claim 4, wherein said layered product is incorporated into described internal layer fabric.
6. the clothes of claim 1, wherein said film is selected from ePTFE and microporous barrier.
7. the clothes of claim 1, wherein said film is incorporated into described nanometer fiber net by following method, described method be selected from solvent combination, adhesive combination, thermal, ultrasonic wave in conjunction with and their combination.
8. the clothes of claim 2, wherein said layered product is incorporated into described outer fabric by following method, described method be selected from loop bonding, adhesive combination, thermal, ultrasonic wave in conjunction with and their combination.
9. the clothes of claim 5, wherein said layered product is incorporated into described internal layer fabric by following method, described method be selected from loop bonding, adhesive combination, thermal, ultrasonic wave in conjunction with and their combination.
10. the clothes of claim 1, wherein said outer fabric comprises weaving material, and described weaving material is selected from nylon, cotton, polyester, polyacrylic, polypropylene and their combination.
11. the clothes of claim 1, wherein said internal layer fabric comprises weaving material, and described weaving material is selected from nylon, cotton, polyester, polyacrylic, polypropylene and their combination.
12. each clothes in the claim 1,5,8 or 9, wherein said layered product and described tissue layer are bonded to each other on their part surface.
13. the clothes of claim 6, wherein said film are to use polyurethane binder to be attached to ePTFE on the described outer fabric.
14. the clothes of claim 1, wherein said nanometer fiber net comprises the nanofiber of polymer, and described polymer is selected from the polysulfone polymer of polyacetals, polyamide, polyester, cellulose ether, cellulose esters, polyalkylene sulphur, poly (arylene ether) oxygen, polysulfones, modification and their mixture.
15. the clothes of claim 1, wherein said nanometer fiber net comprises the nanofiber of polymer, and described polymer is selected from the polymer of following crosslinked and non-crosslinked form: poly-(vinyl chloride), polymethyl methacrylate, polystyrene and their copolymer, poly-(vinylidene fluoride), poly-(vinylidene chloride), polyvinyl alcohol.
16. the clothes of claim 14, wherein said layers of nanofibers comprises polyamide nanofiber, and described polyamide nanofiber is selected from nylon-6, nylon-6,6 and nylon 6, and 6-6,10.
17. the clothes of claim 1, wherein said nanometer fiber net is through calendering.
18. the clothes of claim 1, wherein said nanometer fiber net are oleophobic or hydrophobic.
19. the clothes of claim 1, described clothes also comprise the pad scrim that is combined between described microporous barrier and the described outer tissue layer.
20. the clothes of claim 1, wherein said nanometer fiber net also comprises antistatic additive.
21. the clothes of claim 1, wherein said outer fabric are supatex fabric.
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CN103859666A (en) * 2012-12-14 2014-06-18 东丽纤维研究所（中国）有限公司 Fabric for knitted jacket
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US20090123713A1 (en) 2009-05-14
KR20100108515A (en) 2010-10-07
JP2011503385A (en) 2011-01-27
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WO2009064841A1 (en) 2009-05-22
CN101855069B (en) 2014-05-28

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